Multicolored electrochromic polymer compositions and methods of making and using the same

ABSTRACT

Electrochromic polymers include conjugated chromophores in spaced relation with one another, and conjugation-break spacers (CBSs). At least one CBS separates adjacent chromophores. The chromophores may be colored in the neutral state, and multicolored to transmissive in different oxidization states.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/965,483, filed on Apr. 27, 2018, now allowed, which is a continuationapplication of U.S. application Ser. No. 15/399,839, filed on Jan. 6,2017, now U.S. Pat. No. 9,975,989, which claims priority to U.S.Provisional Application No. 62/331,760, filed on May 4, 2016, titled“Multicolored Electrochromic Polymer Compositions and Methods of Makingand Using the Same.” The entire contents of the above-referencedapplications are incorporated herein by reference.

FIELD OF THE INVENTION

The disclosure relates generally to multicolored electrochromicpolymers, and methods of making and using the same.

BACKGROUND

Electrochromism generally refers to the reversible change in the opticalproperties of a material upon application of a potential. In particular,electrochromic materials exhibit a reversible color change due to anelectrochemical reduction-oxidation (redox) reaction caused byapplication of an electric field.

Conductive, conjugated polymers have become a useful class ofelectrochromic materials in a variety of applications, includingphotovoltaic devices, field effect transistors, organic light emittingdiodes, general printed electronics, anti-glare window and displaysystems, etc. Conjugated polymers have garnered interest due to theability to tune the optical and electronic properties thereof.

However, a need exists to develop new and/or improved polymericmaterials with specific optical and electronic properties, lowerbandgaps, improved color retention, etc. Likewise, there is also a needto develop new and/or improved methods of making said polymericmaterials that involve cost effective, efficient processes with highbatch reproducibility.

BRIEF SUMMARY

The present disclosure is directed to an electrochromic polymer. In oneembodiment, the electrochromic polymer includes a plurality ofπ-conjugated chromophores in spaced relation with one another, whereeach chromophore is colored in a neutral state, and is colored ortransmissive in an oxidized state. The electrochromic polymer alsoincludes a plurality of conjugation-break spacers (CBSs), where at leastone CBS separates adjacent chromophores.

The present disclosure is also directed to a method for preparing atleast a portion of an electrochromic polymer. In one embodiment, themethod for preparing at least a portion of an electrochromic polymerincludes: combining three or more monomer units in a solvent, whereinthe monomer units have complementary reactive functional groups;optionally adding a catalyst to the solvent; and cross-coupling themonomer units to yield a π-conjugated copolymer sequence.

Other objects, features and advantages of the described preferredembodiments will become apparent to those skilled in the art from thefollowing detailed description. It is to be understood, however, thatthe detailed description and specific examples, while indicatingpreferred embodiments of the present invention, are given by way ofillustration and not limitation. Many changes and modifications withinthe scope of the present invention may be made without departing fromthe spirit thereof, and the invention includes all such modifications.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred and non-limiting embodiments of the invention may be morereadily understood by referring to the accompanying drawings in which:

FIG. 1A is a simplified schematic of an electrochromic polymer having aplurality of chromophores separated by at least one conjugation-breakspacer (CBS), according to one exemplary embodiment.

FIG. 1B is an exploded view of a single chromophore positioned betweentwo CBSs, according to one exemplary embodiment.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments of theinvention. However, one skilled in the art will understand that theinvention may be practiced without these details. Moreover, whilevarious embodiments of the invention are disclosed herein, manyadaptations and modifications may be made within the scope of theinvention in accordance with the common general knowledge of thoseskilled in this art. Such modifications include the substitution ofknown equivalents for any aspect of the invention in order to achievethe same result in substantially the same way.

Unless the context requires otherwise, throughout the presentspecification and claims, the word “comprise” and variations thereof,such as, “comprises” and “comprising” are to be construed in an open,inclusive sense, that is as “including, but not limited to.” Numericranges are also inclusive of the numbers defining the range.Additionally, the singular forms “a”, “an” and “the” include pluralreferents unless the context clearly dictates otherwise.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment of the present invention. Thus, the appearances of thephrases “in one embodiment” or “in an embodiment” in various placesthroughout this specification are not necessarily all referring to thesame embodiment, but may be in some instances. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which this invention belongs. For instance, “amino” refers to the—NH₂ radical; “hydroxy” or “hydroxyl” refers to the OH radical; “thioxo”refers to the ═S substituent, etc.

Alkyl” refers to a straight or branched hydrocarbon chain radicalconsisting solely of carbon (C) and hydrogen (H) atoms, which issaturated or unsaturated (i.e., contains one or more double and/ortriple bonds), having from 1 to 30 carbon atoms (C₁-C₃₀ alkyl), andwhich is attached to the rest of the molecule by a single bond, e.g.,methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, n-pentyl,1,1-dimethylethyl (t-butyl), 3-methylhexyl, 2-methylhexyl, ethenyl,prop-1-enyl, but-1-enyl, pent-1-enyl, penta-1,4-dienyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, and the like. Unless statedotherwise specifically in the specification, an alkyl group may beoptionally substituted.

“Alkylene” or “alkylene chain” refers to a straight or branched divalenthydrocarbon chain linking the rest of the molecule to a radical group,consisting solely of carbon and hydrogen, which is saturated orunsaturated (i.e., contains one or more double and/or triple bonds), andhaving from 2 to 30 carbon atoms (C₂-C₃₀ alkylene), e.g., methylene,ethylene, propylene, n-butylene, ethenylene, propenylene, n-butenylene,propynylene, n-butynylene, and the like. The alkylene chain is attachedto the rest of the molecule through a single or double bond and to theradical group through a single or double bond. The points of attachmentof the alkylene chain to the rest of the molecule and to the radicalgroup can be through one carbon or any two carbons within the chain.Unless stated otherwise specifically in the specification, an alkylenechain may be optionally substituted.

“Alkylcarbonyl” refers to a radical of the formula —(C═O)R_(a) whereR_(a) is a C₁-C₃₀ alkyl radical as defined above. Unless statedotherwise specifically in the specification, an alkylcarbonyl group maybe optionally substituted.

“Alkoxy” refers to a radical of the formula —OR_(a) where R_(a) is aC₁-C₃₀ alkyl radical as defined above. A “haloalkoxy” is an alkoxy groupas defined above, wherein at least one carbon-hydrogen bond is replacedwith a carbon-halogen bond. Unless stated otherwise specifically in thespecification, an alkoxy or haloalkoxy group may be optionallysubstituted.

“Alkoxyalkyl” refers to a radical of the formula —R_(b)OR_(a) whereR_(a) is a C₁-C₃₀ alkyl radical as defined above, and R_(b) is a C₂-C₃₀alkylene radical as defined above. A “haloalkoxyalkyl” group is analkoxyalkyl, wherein at least one carbon-hydrogen bond is replaced witha carbon-halogen bond. Unless stated otherwise specifically in thespecification, an alkoxyalkyl or haloalkoxyalkyl group may be optionallysubstituted.

“Alkoxycarbonyl” refers to a radical of the formula —(C═O)OR_(a) whereR_(a) is a C₁-C₃₀ alkyl radical as defined above. Unless statedotherwise specifically in the specification, an alkoxycarbonyl group maybe optionally substituted.

“Alkoxycarbonylalkyl” refers to a radical of the formula—R_(b)(C═O)OR_(a) where R_(a) is a C₁-C₃₀ alkyl radical as definedabove, and R_(b) is a C₂-C₃₀ alkylene as defined above. Unless statedotherwise specifically in the specification, an alkoxycarbonylalkylgroup may be optionally substituted.

“Aminylcarbonyl” refers to a radical of the formula —(C═O)N(R_(a))₂,where each R_(a) is independently H or a C₁-C₃₀ alkyl group as definedabove. Unless stated otherwise specifically in the specification, anaminylcarbonyl group may be optionally substituted.

“Aminylalkyl” refers to a radical of the formula —R_(a)N(R_(b))₂ whereR_(a) is a C₂-C₃₀ alkylene as defined above, and each R_(b) isindependently a C₁-C₃₀ alkyl radical as defined above. Unless statedotherwise specifically in the specification, an aminylalky group may beoptionally substituted.

“Alkylaminyl” refers to a radical of the formula —NHR_(a) or—NR_(a)R_(a) where each R_(a) is independently a C₁-C₃₀ alkyl radical asdefined above, and R_(a) is a C₁-C₃₀ alkyl radical as defined above.Unless stated otherwise specifically in the specification, an aminylalkygroup may be optionally substituted.

“Alkylsulfonyl” refers to a radical of the formula —S(O)₂R_(a) whereR_(a) is a C₁-C₃₀ alkyl radical as defined above. Unless statedotherwise specifically in the specification, an alkylsulfonyl group maybe optionally substituted.

“Alkylsulfonylalkyl” refers to a radical of the formula —R_(b)S(O)₂R_(a)where R_(a) is a C₁-C₃₀ alkyl radical as defined above, and R_(b), is aC₂-C₃₀ alkylene radical as defined above. Unless stated otherwisespecifically in the specification, an alkylsulfonylalkyl group may beoptionally substituted.

“Cyanoalkyl” is a C₁-C₃₀ alkyl group as defined above, wherein at leastone carbon-hydrogen bond is replaced with a carbon-cyano bond. Unlessstated otherwise specifically in the specification, a cyanoalkyl groupmay be optionally substituted.

“Hydroxylalkyl” refers to a C₁-C₃₀ alkyl radical as defined above, whichhas been substituted by one or more hydroxyl groups. Unless statedotherwise specifically in the specification, a hydroxylalkyl group maybe optionally substituted.

“Aryl” refers to a hydrocarbon ring system radical comprising hydrogen,6 to 18 carbon atoms and at least one aromatic ring. For purposes ofthis invention, the aryl radical may be a monocyclic, bicyclic,tricyclic or tetracyclic ring system, which may include fused or bridgedring systems. Aryl radicals include, but are not limited to, arylradicals derived from phenyl, naphthyl, anthryl, etc. Unless statedotherwise specifically in the specification, the term “aryl” is meant toinclude aryl radicals that are optionally substituted.

“Conjugated polymer” refers to a polymer having alternating single anddouble (or triple) carbon-carbon bonds along at least a portion of thepolymer backbone.

“Cycloalkyl” or “carbocyclic ring” refers to a stable non-aromaticmonocyclic or polycyclic hydrocarbon radical consisting solely of carbonand hydrogen atoms, which may include fused or bridged ring systems,having from 3 to 15 carbon atoms, and which is saturated or unsaturatedand attached to the rest of the molecule by a single bond. Monocyclicradicals may include, but are not limited to, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Polycyclicradicals may include, but are not limited to, adamantyl, norbornyl,decalinyl, 7,7-dimethyl-bicyclo[2.2.1]heptanyl, and the like. Unlessotherwise stated specifically in the specification, a cycloalkyl groupmay be optionally substituted.

“Cycloalkylaminyl” refers to a radical of the formula —NR_(a)R_(c) whereR_(a) is, independently, H or a C₁-C₃₀ alkyl radical as defined above,and R_(c) is a C₃-C₁₅ cycloalkyl radical as defined above. Unless statedotherwise specifically in the specification, an aminylalky group may beoptionally substituted.

“Cycloalkylalkylaminyl” refers to a radical of the formula—NR_(a)R_(b)—R_(c) where R_(a) is independently H or a C₁-C₃₀ alkylradical as defined above, R_(b) is a C₂-C₃₀ alkylene radical as definedabove, and R_(c) is a C₃-C₁₅ cycloalkyl radical as defined above. Unlessstated otherwise specifically in the specification, acycloalkylalkylaminyl group may be optionally substituted.

“Cycloalkylalkyl” refers to a radical of the formula —R_(b)R_(c) whereR_(b) is a C₂-C₃₀ alkylene chain as defined above, and R_(c) is a C₃-C₁₅cycloalkyl radical as defined above. Unless stated otherwisespecifically in the specification, a cycloalkylalkyl group may beoptionally substituted.

“Cycloalkylalkyloxy” refers to a radical of the formula —OR_(b)R_(c)where R_(b) is a C₂-C₃₀ alkylene chain as defined above, and R_(c) is aC₃-C₁₅ cycloalkyl radical as defined above. Unless stated otherwisespecifically in the specification, a cycloalkylalkyloxy group may beoptionally substituted.

“Fused” refers to any ring structure described herein which is fused toan existing ring structure in the compounds of the invention. When thefused ring is a heterocyclyl ring or a heteroaryl ring, any carbon atomon the existing ring structure which becomes part of the fusedheterocyclyl ring or the fused heteroaryl ring may be replaced with anitrogen atom.

“Halo” or “halogen” refers to bromo, chloro, fluoro or iodo.

“Haloalkyl” refers to a C₁-C₃₀ alkyl radical as defined above, that issubstituted by one or more halo radicals as defined above, e.g.,trifluoromethyl, difluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl,1,2-difluoroethyl, 3-bromo-2-fluoropropyl, 1,2-dibromoethyl, and thelike. Unless stated otherwise specifically in the specification, ahaloalkyl group may be optionally substituted.

“Heterocyclyl” or “heterocyclic ring” refers to a stable 3- to18-membered non-aromatic ring radical which consists of 2 to 12 carbonatoms and from 1 to 6 heteroatoms selected from the group consisting ofnitrogen, oxygen and sulfur. Unless stated otherwise specifically in thespecification, the heterocyclyl radical may be a monocyclic, bicyclic,tricyclic or tetracyclic ring system, which may include fused or bridgedring systems; and the nitrogen, carbon or sulfur atoms in theheterocyclyl radical may be optionally oxidized; the nitrogen atom maybe optionally quaternized; and the heterocyclyl radical may be partiallyor fully saturated. Examples of such heterocyclyl radicals may include,but are not limited to, dioxolanyl, thienyl[1,3]dithianyl,decahydroisoquinolyl, imidazolinyl, imidazolidinyl, isothiazolidinyl,isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl,2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, oxazolidinyl,piperidinyl, piperazinyl, 4-piperidonyl, pyrrolidinyl, pyrazolidinyl,quinuclidinyl, thiazolidinyl, tetrahydrofuryl, trithianyl,tetrahydropyranyl, thiomorpholinyl, thiamorpholinyl,1-oxo-thiomorpholinyl, and 1,1-dioxo-thiomorpholinyl. Unless statedotherwise specifically in the specification, Unless stated otherwisespecifically in the specification, a heterocyclyl group may beoptionally substituted.

“Heterocyclyloxy” refers to a radical of the formula —OR_(d), whereinR_(d) is a C₁-C₁₂ heterocyclyl radical as defined above. Unless statedotherwise specifically in the specification, a heterocyclyloxy group maybe optionally substituted.

“Heterocyclylalkyloxy” refers to a radical of the formula —OR_(b)R_(d)where R_(b) is a C₂-C₃₀ alkylene chain as defined above, and R_(d) is aC₁-C₁₂ heterocyclyl radical as defined above. Unless stated otherwisespecifically in the specification, a heterocyclylalkyloxy group may beoptionally substituted.

“Heterocyclylaminyl” refers to a radical of the formula —N(R_(a))₂R_(d)where R_(a) is independently H or a C₁-C₃₀ alkyl radical as definedabove, and R_(d) is a C₁-C₁₂ heterocyclyl radical as defined above.Unless stated otherwise specifically in the specification, aheterocyclylaminyl group may be optionally substituted.

“Heterocyclylalkylaminyl” refers to a radical of the formula—NR_(a)R_(b)—R_(d) where R_(a) is H or a C₁-C₃₀ alkyl radical as definedabove, R_(b) is a C₂-C₃₀ alkylene radical as defined above, and R_(d) isa C₁-C₁₂ heterocyclyl radical as defined above. Unless stated otherwisespecifically in the specification, a cycloalkylalkylaminyl group may beoptionally substituted.

“Heterocyclylcarbonyl” refers to a radical of the formula —C(═O)R_(d)where R_(d) is a C₁-C₁₂ heterocyclyl radical as defined above. Unlessstated otherwise specifically in the specification, aheterocyclycarbonyl group may be optionally substituted.

“Heterocyclylalkyl” refers to a radical of the formula —R_(b)R_(d) whereR_(b) is a C₂-C₃₀ alkylene chain as defined above, and R_(d) is a C₁-C₁₂heterocyclyl radical as defined above. Unless stated otherwisespecifically in the specification, a heterocyclylalkyl group may beoptionally substituted.

“Heteroaryl” refers to a 5 to 14 membered ring system radical comprisinghydrogen atoms, 1 to 13 carbon atoms, 1 to 6 heteroatoms selected fromthe group consisting of nitrogen, oxygen and sulfur, and at least onearomatic ring. For purposes of this invention, the heteroaryl radicalmay be a monocyclic, bicyclic, tricyclic or tetracyclic ring system,which may include fused or bridged ring systems; and the nitrogen,carbon or sulfur atoms in the heteroaryl radical may be optionallyoxidized; the nitrogen atom may be optionally quaternized. Examplesinclude, but are not limited to, azepinyl, acridinyl, benzimidazolyl,benzothiazolyl, benzindolyl, benzodioxolyl, benzofuranyl, benzooxazolyl,benzothiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepinyl,1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl,benzodioxinyl, benzopyranyl, benzopyranonyl, benzofuranyl,benzofuranonyl, benzothienyl (benzothiophenyl), benzotriazolyl,benzo[4,6]imidazo[1,2-a]pyridinyl, carbazolyl, cinnolinyl,dibenzofuranyl, dibenzothiophenyl, furanyl, furanonyl, isothiazolyl,imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, indolinyl,isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl, naphthyridinyl,oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 1-oxidopyridinyl,1-oxidopyrimidinyl, 1-oxidopyrazinyl, 1-oxidopyridazinyl,1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl,phthalazinyl, pteridinyl, purinyl, pyrrolyl, pyrazolyl, pyridinyl,pyrazinyl, pyrimidinyl, pyridazinyl, quinazolinyl, quinoxalinyl,quinolinyl, quinuclidinyl, isoquinolinyl, tetrahydroquinolinyl,thiazolyl, thiadiazolyl, triazolyl, tetrazolyl, triazinyl, andthiophenyl (i.e. thienyl). Unless stated otherwise specifically in thespecification, a heteroaryl group may be optionally substituted.

“Heteroarylalkyl” refers to a radical of the formula —R_(b)R_(e) whereR_(b) is a C₂-C₃₀ alkylene chain as defined above, and R_(e) is a C₁-C₁₃heteroaryl radical as defined above. Unless stated otherwisespecifically in the specification, a heteroarylalkyl group may beoptionally substituted.

The term “substituted” used herein means any of the above groups (e.g.,alkyl, alkylene, alkylcarbonyl, alkoxy, alkoxyalkyl, haloalkoxyalkyl,alkoxycarbonyl, alkoxycarbonylalkyl, aminylcarbonyl, aminylalkyl,alkylaminyl, alkylsulfonyl, alkylsulfonylalkyl, cyanoalkyl,hydroxylalkyl, aryl, cycloalkyl, cycloalkylalkyl, cycloalkyloxy,cycloalkylaminyl, cycloalkylalkylaminyl, cycloalkylalkyloxy, haloalkyl,heterocyclyl, heterocyclyloxy, heterocyclylalkyloxy, heterocyclylaminyl,heterocyclylalkylaminyl, heterocyclylcarbonyl, heterocyclylalkyl,heteroaryl and/or heteroarylalkyl) wherein at least one hydrogen atom isreplaced by a bond to a non-hydrogen atoms such as, but not limited to:a halogen atom such as F, Cl, Br, and I; an oxygen atom in groups suchas hydroxyl groups, alkoxy groups, and ester groups; a sulfur atom ingroups such as thiol groups, thioalkyl groups, sulfone groups, sulfonylgroups, and sulfoxide groups; a nitrogen atom in groups such as amines,amides, alkylamines, dialkylamines, arylamines, alkylarylamines,diarylamines, N-oxides, imides, and enamines; a silicon atom in groupssuch as trialkylsilyl groups, dialkylarylsilyl groups, alkyldiarylsilylgroups, and triarylsilyl groups; and other heteroatoms in various othergroups. “Substituted” also means any of the above groups in which one ormore hydrogen atoms are replaced by a higher-order bond (e.g., a double-or triple-bond) to a heteroatom such as oxygen in oxo, carbonyl,carboxyl, and ester groups; and nitrogen in groups such as imines,oximes, hydrazones, and nitriles. For example, “substituted” includesany of the above groups in which one or more hydrogen atoms are replacedwith —NR_(g)R_(h), —NR_(g)C(═O)R_(h), —NR_(g)C(═O)NR_(g)R_(h),—NR_(g)C(═O)OR_(h), —NR_(g)SO₂R_(h), —OC(═O)NR_(g)R_(h), —OR_(g),—SR_(g), —SOR_(g), —SO₂R_(g), —OSO₂R_(g), —SO₂OR_(g), ═NSO₂R_(g), and—SO₂NR_(g)R_(h). “Substituted also means any of the above groups inwhich one or more hydrogen atoms are replaced with —C(═O)R_(g),—C(═O)OR_(g), —C(═O)NR_(g)R_(h), —CH₂SO₂R_(g), —CH₂SO₂NR_(g)R_(h). Inthe foregoing, R_(g) and R_(h) are the same or different andindependently hydrogen, alkyl, alkoxy, alkylaminyl, thioalkyl, aryl,aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl,N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl and/orheteroarylalkyl. “Substituted” further means any of the above groups inwhich one or more hydrogen atoms are replaced by a bond to an amino,alkylaminyl, cyano, hydroxyl, imino, nitro, oxo, thioxo, halo, alkyl,alkoxy, alkylaminyl, thioalkyl, aryl, aralkyl, cycloalkyl,cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl,heterocyclylalkyl, heteroaryl, N-heteroaryl and/or heteroarylalkylgroup. In addition, each of the foregoing substituents may also beoptionally substituted with one or more of the above substituents.

“Optional” or “optionally” means that the subsequently described eventof circumstances may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances in whichit does not. For example, “optionally substituted aryl” means that thearyl radical may or may not be substituted and that the descriptionincludes both substituted aryl radicals and aryl radicals having nosubstitution.

Embodiments disclosed herein are directed to novel semiconductingelectrochromic polymers that exhibit high optical contrasts in thevisible region, as well as possess switching speeds and/or stabilityoften superior to current electrochromic polymers (ECPs). The novelsemiconducting electrochromic polymers may include a plurality ofπ-conjugated chromophores, one or more of which may be colored in theneutral state and colored or transmissive in an oxidized state, and aplurality of conjugation-break spacers (CBS), where at least one CBSseparates adjacent chromophores. Such semiconducting electrochromicpolymers may be melt-processable, with the melting temperatures used insuch processes being controlled by the ratio of CBSs with selectedchromophores. These multicolored electrochromic polymers may thus beparticularly advantageous for organic electronic devices due to theirsuperior and/or improved processibility, optoelectronic properties, andmechanical properties.

Referring now to FIG. 1A, a simplified schematic of an electrochromicpolymer 100 is shown according to an exemplary embodiment. Theelectrochromic polymer 100 of FIG. 1A may be implemented in combinationwith other devices/features/components described herein, such as thosedescribed with reference to other embodiments and/or FIGS. Theelectrochromic polymer 100 may also be used in various applicationsand/or in permutations, which may or may not be noted in theillustrative embodiments/aspects described herein. For instance, theelectrochromic polymer 100 may include more or less features/componentsthan those shown in FIG. 1A, in certain embodiments.

As shown in FIG. 1A, the electrochromic polymer 100 includes a pluralityof π-conjugated chromophores 102 in spaced relation with one another.Adjacent chromophores are separated from one another by at least oneconjugation-break spacer (CBS) 104. Accordingly, the electrochromicpolymer 100 has the structure:-{[(C1)(CBS1)]_(n1)-[(C2)(CBS2)]_(n2)-[(C3)(CBS3)]_(n3)-[(C4)(CBS4)]_(n4)}-,where C₁, C₂, C₃, and C₄ represent the π-conjugated chromophores 104;CBS1, CBS2, CBS3, and CBS4 represent the non-conjugated, flexiblespacers 104; and each of n1, n2, n3, and n4 is independently an integerin a range from 1 to 50.

In certain embodiments, each chromophore 102 may independently include arandom or alternating copolymer sequence. For instance, each chromophore102 may independently include at least two discernable monomer unitsthat are randomly distributed to yield a random copolymer sequence, ordistributed in a regular alternating fashion to yield an alternatingcopolymer sequence.

In certain embodiments, the aforementioned monomer units may eachinclude a single aromatic ring, a single heteroaromatic ring, aplurality of fused aromatic rings, and/or a plurality of fusedheteroaromatic rings. For instance, in one embodiment, at least one ofthe monomer units may include a thiophene unit or a substitutedthiophene unit, such as 3,4-propylenedioxythiophene substituted on thepropylene bridge, or any derivative and/or equivalent analog thereof. Inanother embodiment, at least another of the monomer units may include amonocyclic or fused polycyclic aromatic unit, such as benzene,substituted benzene, benzo[c][1,2,5]thiadiazole, substitutedbenzo[c][1,2,5]thiadiazole, or any derivative and/or equivalent analogthereof.

In certain embodiments, at least one of the monomer units may includeone or more substituents (e.g., functional groups, side chains, etc.)configured to provide sufficient solubility, desired electronicproperties, and/or desired steric and molecular stacking properties.Solubilizing substituents may include linear or branched alkyl groups,which may improve polymer solubility in organic solvents. Solubilizingsubstituents may also include polar or ionic groups (e.g., ether, ester,amide, sulfonate, carboxylate, phosphonate, amine functionalized chains,etc.), which may improve polymer solubility in aqueous solvents. Theinclusion of suitable polar or ionic substituents in at least one of themonomer units may also facilitate the copolymer's ability to adhere tosurfaces, e.g., metallic surfaces. In certain embodiments, at least oneof the monomer units may include one or more substituents configured tofacilitate the processing of the copolymer into a film, and the optionalconversion of the copolymer into a different copolymer (e.g., conversionfrom a soluble film to an insoluble film).

In certain embodiments, at least one chromophore 102 may include aconjugated copolymer sequence having the structure (I):

where m is an integer greater than 0 (e.g., an integer in a range from 1to 50), and each of R₁, R₂, R₃ and R₄ is independently selected fromhydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl,C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl,C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl,C₆-C₁₈ aryl, C₃-C₁₈ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

In certain embodiments, at least one chromophore 102 may include aconjugated copolymer sequence having the structure (II):

where m is an integer greater than 0 (e.g., an integer in a range from 1to 50), and each of R₁, R₂, R₃ R₄, R₅ and R₆ is independently selectedfrom hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl,C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl,C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl,C₆-C₁₈ aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

In certain embodiments, at least one chromophore 102 may include aconjugated copolymer sequence having the structure (III):

where m is an integer greater than 0 (e.g., an integer in a range from 1to 50), and each of R₁, R₂, R₃, R₄, R₅ and R₆ is independently selectedfrom hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl,C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl,C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl,C₆-C₁₈ aryl, C₃-C₁₈ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

As noted above, the integer m in structures (I), (II), and/or (III) mayrange from 1 to 50 in certain embodiments. In one embodiment, theinteger m in structures (I), (II), and/or (III) may range from 2 to 50,3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to 50, 20 to 50, 25 to 50, 30 to50, 35 to 50, 40 to 50, 45 to 50, 1 to 40, 2 to 40, 3 to 40, 5 to 40, 8to 40, 10 to 40, 15 to 40, 20 to 40, 25 to 40, 30 to 40, 35 to 40, 1 to30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10 to 30, 15 to 30, 20 to 30, 25to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20, 8 to 20, 10 to 20, 15 to 20,1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to 10, 1 to 5, 2 to 5, or 3 to 5.

In certain embodiments, each of the chromophores 102 of theelectrochromic polymer 100 may independently include a conjugatedcopolymer sequence having structure (I), structure (II), structure(III), or combinations thereof. For instance, in one embodiment, each ofthe chromophores 102 may include a conjugated copolymer sequence havingstructure (I). In another embodiment, each of the chromophores 102 mayinclude a conjugated copolymer sequence having structure (II). In yetanother embodiment, each of the chromophores 102 may include aconjugated copolymer sequence having structure (III). In still anotherembodiment, each of the chromophores 102 may include a conjugatedcopolymer sequence resulting from a combination of structures (I) and(II), a combination of structures (I) and (III), a combination ofstructures (II) and (III), or a combination of structures (I), (II) and(III).

In certain embodiments, at least two chromophores 102 may includeconjugated copolymer sequences having different structures relative toone another. For instance, in one embodiment, at least one of thechromophores 102 may include a conjugated copolymer sequence havingstructure (I), whereas at least another of the chromophores 102 mayinclude a conjugated sequence having structure (II) or (III). Likewise,in one embodiment, at least one of the chromophores 102 may include aconjugated copolymer sequence having structure (II), whereas at leastanother of the chromophores 102 may include a conjugated sequence havingstructure (III). In another embodiment, at least one of the chromophores102 may include a conjugated copolymer sequence having structure (I), atleast one of the chromophores 102 may include a conjugated sequencehaving structure (II), and at least one of the chromophores 102 mayinclude a conjugated sequence having structure (III).

In certain embodiments, each of the chromophores 102 may be colored(e.g., red, green, blue, or other color) in the neutral state. Thedesired color of each chromophore 102 may be achieved, in variousembodiments, by varying the conjugated copolymer sequence thereof.

In one embodiment, one or more of the chromophores 102 may be adifferent color relative to one another in a neutral state. In oneembodiment, at least two (e.g., two, three, four, five, six, seven,eight, etc.) of the chromophores 102 may be a different color relativeto one another in a neutral state. In one embodiment, at least amajority or substantially all (e.g., at least 80%, 85%, 90%, 95% or 99%)of the chromophores 102 may be a different color relative to one anotherin a neutral state. In one embodiment, each the chromophores 102 may bea different color relative to one another in a neutral state.

In another embodiment, at least two of the chromophores 102 may have thesame color as one another in a neutral state. In one embodiment, atleast a majority or substantially all of the chromophores 102 may havethe same color as one another in a neutral state. In one embodiment,each of the chromophores 102 may have the same color as one another in aneutral state.

In certain embodiments, each of the chromophores 102 may be colored ortransmissive in an oxidation state. In one embodiment, at least one ofthe chromophores 102 may be transmissive in an oxidation state. In oneembodiment, at least a majority or substantially all of the chromophores102 may be transmissive in an oxidation state. In one embodiment, eachof the chromophores 102 may be transmissive in an oxidation state.

In another embodiment, at least one of the chromophores 102 may becolored in an oxidation state. In one embodiment, at least a majority orsubstantially all of the chromophores 102 may be colored in an oxidationstate. In one embodiment, each of the chromophores 102 may be colored inan oxidation state.

In yet another embodiment, at least one of the chromophores 102 may betransmissive in an oxidation state, and at least another of thechromophores 102 may be colored in an oxidation state.

In certain embodiments, at least one chromophore 102 may have severalstable oxidation states of different colors. In one embodiment, at leasta majority or substantially all of the chromophores 102 may have severalstable oxidation states of different colors. In one embodiment, each ofthe chromophores 102 may have several stable oxidation states ofdifferent colors.

In certain embodiments, at least two, at least a majority, substantiallyall, or all of the chromophores 102 in the electrochromic polymer 100may have one or more of the following: the same structure, the sameoptoelectronic properties (e.g., exhibit the same color in the neutralstate, exhibit the same color(s) or be transmissive in the redoxstate(s), etc.), the same density, the same processibility, the samesolubility, the same flexibility, and the same mechanical properties asone another.

In certain embodiments, at least two, at least a majority, substantiallyall, or all of the chromophores 102 in the electrochromic polymer 100may have one or more of the following: different compositions, differentoptoelectronic properties (e.g., exhibit different colors in the neutralstate, exhibit different colors or be transmissive in the oxidizedstate(s), etc.), different densities, different processibility,different solubility, different flexibility, and different mechanicalproperties as one another.

In certain embodiments, the conjugated copolymer sequences of thechromophores 102 may be prepared by step-growth, condensation reactionsbetween monomers comprising complementary reactive groups. Skilledartisans may readily appreciate the complementary reactive groups forthe monomers which are suitable to achieve polymerization viacondensation reactions or other known polymerization reactions. Suchcondensation reactions may occur in an appropriate solvent, and beoptionally catalyzed by a palladium or other metallic catalyst. Suitablecondensation reactions may include Suzuki coupling, Kuamda coupling,Negishi coupling, Stille coupling, etc.

As discussed previously, at least one CBS 104 (designated by the symbol

in FIG. 1A) separates adjacent chromophores 102. Each of the CBSs 104may be flexible, and non-conjugated. The presence of the CBSs 104 in theelectrochromic polymer 100 may serve to confine the conjugation of thechromophores 100 into a well-defined chain length. Moreover, theelectrochromic polymer 100 may also be melt-processable, with the ratioof the CBSs with selected chromophores controlling the meltingtemperatures. The ratio of the CBSs with selected chromophores may, insome embodiments, depend on the CBS and/or the chromophore length.

An exploded view of a single chromophore 102 having a CBS 104 on eitherside thereof is shown in FIG. 1B. In certain embodiments, the CBS 104 oneither side of the chromophore 102 may be the same as one another (e.g.,have the same structure). In certain embodiments, the CBS the CBS 104 oneither side of the chromophore 102 may different from one another (e.g.,have different structures). In certain embodiments, the CBS 104 on oneor both sides of the chromophore may have one of the followingstructures (IV), (V), (VI), (VII), or (VIII):

or combinations thereof, where each of x, y, and z is independently aninteger in a range from 1 to 12, 2 to 12, 4 to 12, 6 to 12, 8 to 12, 10to 12, 1 to 10, 2 to 10, 4 to 10, 6 to 10, 8 to 10, 1 to 8, 2 to 8, 4 to8, 6 to 8, 1 to 6, 2 to 6, 4 to 6, 1 to 4, or 2 to 4.

In certain embodiments, the CBS 104 may have terminal functional groups(designated B₁ and B₂ in FIG. 1B), each of which may independentlyinclude, but is not limited to, OH, NH₂, COOH, phenol, alkene, and thelike.

EXAMPLES

As noted above, the conjugated copolymer sequences of the chromophoresdisclosed herein may be prepared by step-growth, condensation reactionsbetween monomers comprising complementary reactive groups. For instance,in certain embodiments, a conjugated copolymer sequence may be preparedby: (i) combining, in one or more suitable solvents, at least threemonomer units (e.g., M1, M2, M3), where the monomer units havecomplementary reactive groups; (ii) optionally adding a catalyst (e.g.,a palladium compound) to the solvent; and (iii) cross-coupling themonomer units to produce a conjugated copolymer sequence in which themonomer units are distributed in a random fashion or a regularalternating fashion.

In certain embodiments, one of the monomer units (e.g., M1) may include:1,4-dibromobenzene, substituted 1,4-dibromobenzene,4,7-dibromobenzo[c][1,2,5]thiadiazole, or substituted4,7-dibromobenzo[c][1,2,5]thiadiazole. For instance, the structure ofthe M1 monomer unit may be selected from the following structures (IX)or (X):

where each of R₁, R₂, R₃ and R₄ is independently selected from hydrogen,C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl,C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as would be appreciated byskilled artisans upon reading the present disclosure.

In certain embodiments, the structure of at least another of the monomerunits (e.g., M2 and/or M3) may include: 3,4-propylenedioxythiophene, asubstituted 3,4-propylenedioxythiophene, or derivatives and/orcombinations thereof. For instance, the structure of the M2 and/or M3monomer units may be selected from the following structures (XI), (XII)or (XIII):

where each of R₁ and R₂ is independently selected from hydrogen, C₁-C₃₀alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as would be appreciated byskilled artisans upon reading the present disclosure; and L is a linkingsegment. The linking segment, L, may include:

or combinations thereof, where each of x, y, and z is independently aninteger greater than 0. In some embodiments, each of x, y, and z isindependently an integer in a range from 1 to 12. Other suitable linkingsegments may also be used as would be appreciated by skilled artisansupon reading the present disclosure.

Examples 1-6 describe reaction schemes for the preparation of conjugatedcopolymer sequences in accordance with the general polymerization methoddiscussed above. In contrast to conventional electrochromic polymers,the novel electrochromic polymers disclosed herein, such as thosedescribed with reference to FIGS. 1A-1B and Examples 1-6, demonstrateenhanced solution processability, can be melt processed, and exhibitmulti-color transitions upon oxidation or reduction before they arefully oxidized and become transmissive.

Example 1: Preparation of a Conjugated Copolymer Sequence of Structure(XXI)

Monomer units having general structures (IX), (XI) and (XII) arecombined in a suitable solvent in the presence of a palladium catalystto form a terminal alkene of structure (XIX). Terminal alkene (XIX) iscross-coupled with a second terminal alkene having structure (XX) via anacyclic diene metathesis (ADMET) reaction to form the conjugatedcopolymer sequence having structure (XXI).

Each R and R′ in the compounds above independently corresponds to afunctional group as disclosed herein. In one embodiment, each R and R′is independently selected from: C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

Each integer m, z, n1 and n2 in the compounds above is greater thanzero. In one embodiment, integers m, z, n1, and n2 each independentlyrange from 1 to 50, 2 to 50, 3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to50, 20 to 50, 25 to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 1 to 40,2 to 40, 3 to 40, 5 to 40, 8 to 40, 10 to 40, 15 to 40, 20 to 40, 25 to40, 30 to 40, 35 to 40, 1 to 30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10to 30, 15 to 30, 20 to 30, 25 to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20,8 to 20, 10 to 20, 15 to 20, 1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to10, 1 to 5, 2 to 5, or 3 to 5.

Example 2: Preparation of a Conjugated Copolymer Sequence of Structure(XXIII)

Monomer units having general structures (X), (XI) and (XII) are combinedin a suitable solvent in the presence of a palladium catalyst to form aterminal alkene of structure (XXII). Terminal alkene (XXII) iscross-coupled with a second terminal alkene having structure (XX) via anacyclic diene metathesis (ADMET) reaction to form the conjugatedcopolymer sequence having structure (XXIII).

Each R, R′, R″ in the compounds above independently corresponds to afunctional group as disclosed herein. In one embodiment, each R, R′ andR″ is independently selected from: C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

Each integer m, z, n1 and n2 in the compounds above is greater thanzero. In one embodiment, integers m, z, n1, and n2 each independentlyrange from 1 to 50, 2 to 50, 3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to50, 20 to 50, 25 to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 1 to 40,2 to 40, 3 to 40, 5 to 40, 8 to 40, 10 to 40, 15 to 40, 20 to 40, 25 to40, 30 to 40, 35 to 40, 1 to 30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10to 30, 15 to 30, 20 to 30, 25 to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20,8 to 20, 10 to 20, 15 to 20, 1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to10, 1 to 5, 2 to 5, or 3 to 5.

Example 3: Preparation of a Conjugated Copolymer Sequence of Structure(XXIV)

Terminal alkenes having structures (XIX), (XXII) and (XX) arecross-coupled via an acyclic diene metathesis (ADMET) reaction to formthe conjugated copolymer sequence having structure (XXIV).

Each R, R′, R″ in the compounds above independently corresponds to afunctional group as disclosed herein. In one embodiment, each R, R′ andR″ is independently selected from: C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-Cis aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

Each integer m and z in the compounds above is greater than zero. In oneembodiment, integers m and z each independently range from 1 to 50, 2 to50, 3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to 50, 20 to 50, 25 to 50,30 to 50, 35 to 50, 40 to 50, 45 to 50, 1 to 40, 2 to 40, 3 to 40, 5 to40, 8 to 40, 10 to 40, 15 to 40, 20 to 40, 25 to 40, 30 to 40, 35 to 40,1 to 30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10 to 30, 15 to 30, 20 to30, 25 to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20, 8 to 20, 10 to 20, 15to 20, 1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to 10, 1 to 5, 2 to 5, or 3to 5.

Example 4: Preparation of a Conjugated Copolymer Sequence of Structure(XXV)

Monomer units having general structures (IX), (XI) and (XIII) arecombined in a suitable solvent in the presence of a palladium catalystto form a conjugated copolymer sequence having structure (XXV).

Each R and R′ in the compounds above independently corresponds to afunctional group as disclosed herein. In one embodiment, each R and R′is independently selected from: C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

Each integer n1 and n2 in the compounds above is greater than zero. Inone embodiment, integers n1 and n2 each independently range from 1 to50, 2 to 50, 3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to 50, 20 to 50, 25to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 1 to 40, 2 to 40, 3 to40, 5 to 40, 8 to 40, 10 to 40, 15 to 40, 20 to 40, 25 to 40, 30 to 40,35 to 40, 1 to 30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10 to 30, 15 to30, 20 to 30, 25 to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20, 8 to 20, 10to 20, 15 to 20, 1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to 10, 1 to 5, 2to 5, or 3 to 5.

A further exemplary, non-limiting embodiment describing the preparationof a conjugated copolymer sequence having structure (XXV) is as follows.A Schlenk flask (flask I) charged with Pd(OAc)₂ (about 0.02 eq), K₂CO₃(about 2.6 eq), structure IX (about 1 eq) and PivOH (about 0.3 eq) wasevacuated under vacuum for about 10 minutes and then purged withnitrogen. This process was repeated 3 times. To a separate flask (flaskII) charged with structure XI (about 0.65 eq) and structure XIII (about0.35 eq), n-methyl-2-pyrrolidone (NMP) (about 70 mL) was added todissolve the solids. The solution was bubbling with nitrogen gas forabout 15 min. The solution in flask (II) was subsequently transferred toflask (I) using a cannula. Another portion of degassed NMP (about 70 ml)was injected through a septum into flask (II) and then transferred tothe flask (I) using the cannula. The combined solution was immersed intoa heated oil bath at about 140° C. and stirred for about 24 h. Uponcooling to about 60° C., the suspension was poured into a 1M HClmethanol solution (about 600 mL) with stirring. The solids were filteredout and dried. The obtained solids were dissolved into chloroform. Theorganic solution was washed twice with a 1M HCl aqueous solution (about200 mL). The combined organic phase was dried over magnesium sulfate andconcentrated under vacuum before being added dropwise to methanol (about600 mL). The precipitates were filtered and dried to give a blackpolymer of structure (XXV) with a yield of about 60-85%. It was observedthat the polymer of structure (XXV) had surprisingly better solubilityin common organic solvents such as toluene and chloroform than its fullyconjugated counterpart.

Example 5: Preparation of a Conjugated Copolymer Sequence of Structure(XXVI)

Monomer units having general structures (X), (XI) and (XIII) arecombined in a suitable solvent in the presence of a palladium catalystto form a conjugated copolymer sequence having structure (XXVI).

Each R, R′, and R″ in the compounds above independently corresponds to afunctional group as disclosed herein. In one embodiment, each R, R′, andR″ is independently selected from: C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-Cis aryl, C₃-Cis cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

Each integer n1 and n2 in the compounds above is greater than zero. Inone embodiment, integers n1 and n2 each independently range from 1 to50, 2 to 50, 3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to 50, 20 to 50, 25to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 1 to 40, 2 to 40, 3 to40, 5 to 40, 8 to 40, 10 to 40, 15 to 40, 20 to 40, 25 to 40, 30 to 40,35 to 40, 1 to 30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10 to 30, 15 to30, 20 to 30, 25 to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20, 8 to 20, 10to 20, 15 to 20, 1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to 10, 1 to 5, 2to 5, or 3 to 5.

Example 6: Preparation of a Conjugated Copolymer Sequence of Structure(XXVII)

Monomer units having general structures (IX, (X), (XI) and (XIII) arecombined in a suitable solvent in the presence of a palladium catalystto form a conjugated copolymer sequence having structure (XXVII).

Each R, R′, and R″ in the compounds above independently corresponds to afunctional group as disclosed herein. In one embodiment, each R, R′, andR″ is independently selected from: C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-Cis aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, substituted analogs of any of the foregoing, andother such suitable functional group(s) as disclosed herein or as wouldbe appreciated by skilled artisans upon reading the present disclosure.

Each integer n1, n2, n3 and n3 in the compounds above is greater thanzero. In one embodiment, integers n1, n2, n3 and n4 each independentlyrange from 1 to 50, 2 to 50, 3 to 50, 5 to 50, 8 to 50, 10 to 50, 15 to50, 20 to 50, 25 to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 1 to 40,2 to 40, 3 to 40, 5 to 40, 8 to 40, 10 to 40, 15 to 40, 20 to 40, 25 to40, 30 to 40, 35 to 40, 1 to 30, 2 to 30, 3 to 30, 5 to 30, 8 to 30, 10to 30, 15 to 30, 20 to 30, 25 to 30, 1 to 20, 2 to 20, 3 to 20, 5 to 20,8 to 20, 10 to 20, 15 to 20, 1 to 10, 2 to 10, 3 to 10, 5 to 10, 8 to10, 1 to 5, 2 to 5, or 3 to 5.

APPLICATIONS/USES

Embodiments of the multicolored electrochromic polymers disclosed hereinmay be used in various applications, devices, industries etc. Forexample, the multicolored electrochromic polymers may be configured foruse in smart window and display technology, e.g., anti-glare carmirrors, smart windows configured to modulate the transmission orreflected solar radiation for use in cars, aircrafts, buildings, and thelike; protective eyewear; camouflage and/or chameleonic materials;polymer photovoltaic devices; field effect transistors; batteries;supercapacitors; light emitting diodes; and other electrochromic andelectronic devices.

The invention described and claimed herein is not to be limited in scopeby the specific preferred embodiments disclosed herein, as theseembodiments are intended as illustrations of several aspects of theinvention. Indeed, various modifications of the invention in addition tothose shown and described herein will become apparent to those skilledin the art from the foregoing description. Such modifications are alsointended to fall within the scope of the appended claims.

What is claimed is:
 1. A method for preparing at least a portion of anelectrochromic polymer, the method comprising: combining three or moremonomer units in a solvent, wherein the three or more monomer unitscomprise complementary reactive functional groups; and the monomer unitseach comprise an aromatic ring, a heteroaromatic ring, fused aromaticrings, or fused heteroaromatic rings; and cross-coupling the combinedmonomer units to yield π-conjugated copolymer sequences in spacedrelation with one another, each π-conjugated copolymer sequencecomprising at least three of the monomer units; and at least one of theπ-conjugated copolymer sequences comprising

, wherein: m is an integer greater than 0, and each of R₁, R₂, R₃, R₄,R₅ and R₆ is independently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, orsubstituted analogs thereof, and at least one of the adjacentπ-conjugated copolymer sequences is separated by a non-conjugatedflexible spacer.
 2. The method of claim 1, further comprising adding acatalyst comprising a palladium compound to the solvent.
 3. The methodof claim 1, wherein at least one of the three or more monomer units hasa structure of Formula (IX) or (X):

wherein each of R₁, R₂, R₃, and R₄ is independently selected fromhydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl,C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl,C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl,C₆-C₁₈ aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, and substituted analogs thereof.
 4. The methodof claim 1, wherein at least one of the three or more monomer units hasa structure of Formula (XI), (XII), or (XIII)

wherein: each of R₁ and R₂ is independently selected from hydrogen,C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl,C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy, C₃-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, and substituted analogs thereof; and L is alinking segment.
 5. The method of claim 1, wherein the π-conjugatedcopolymer sequence comprises:

wherein: each of z, m, n1, and n2 is independently an integer greaterthan 0; and each of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ isindependently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl,C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs thereof.
 6. The method of claim 1, wherein theπ-conjugated copolymer sequence comprises:

wherein: each of z, m, n1, and n2 is independently an integer greaterthan 0; and each of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ isindependently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl,C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs thereof.
 7. The method of claim 1, wherein theπ-conjugated copolymer sequence comprises:

wherein: each of n1 and n2 is independently an integer greater than 0;and each of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ is independentlyselected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl,C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl, C₂-C₃₀alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀ aminylcarbonyl,C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀ alkylsulfonyl, C₃-C₃₀alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅ cycloalkyl, C₃-C₃₀cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl, C₅-C₃₀ cycloalkylalkyl,C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl, C₁-C₁₂ heterocyclyloxy,C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylaminyl, C₅-C₃₀ heterocyclylalkylaminyl, C₂-C₁₂heterocyclylcarbonyl, C₃-C₃₀ heterocyclylalkyl, C₁-C₁₃ heteroaryl,C₃-C₃₀ heteroarylalkyl, and substituted analogs thereof; and L is alinking segment.
 8. The method of claim 1, wherein the π-conjugatedcopolymer sequence comprises:

wherein: each of n1 and n2 is independently an integer greater than 0;each of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, and R₁₄is independently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl,C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs thereof; and L is a linking segment.
 9. The methodof claim 1, wherein the π-conjugated copolymer sequence comprises:

wherein: each of n1, n2, n3, and n4 is independently an integer greaterthan zero; each of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂,R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃, and R₂₄ isindependently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl,C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs thereof; and L is a linking segment.
 10. Anelectrochromic polymer synthesized from the method of claim 1, whereinat least two of the π-conjugated copolymer sequences are combined intoπ-conjugated chromophores: the π-conjugated chromophores being in spacedrelation with one another, wherein each π-conjugated chromophore iscolored in a neutral state, and is colored or transmissive in anoxidized state; and a plurality of conjugation-break spacers (CBSs),wherein at least one CBS separates adjacent π-conjugated chromophores.11. The electrochromic polymer of claim 10, wherein at least one CBScomprises:

wherein each of x, y, and z is independently an integer in a range from1 to
 12. 12. The electrochromic polymer of claim 10, wherein at leasttwo of the CBSs have the same structure as one another.
 13. Theelectrochromic polymer of claim 10, wherein at least two of the CBSshave a different structure from one another.
 14. The electrochromicpolymer of claim 10, wherein each π-conjugated chromophore comprises arandom copolymer sequence or an alternating copolymer sequence.
 15. Theelectrochromic polymer of claim 10, wherein at least one of theplurality of π-conjugated chromophores comprises a structure of Formula(I):

wherein: m is an integer greater than 0; and each of R₁, R₂, R₃, and R₄is independently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl,C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs of any of the foregoing.
 16. The electrochromicpolymer of claim 10, wherein at least one of the plurality ofπ-conjugated chromophores comprises a structure of Formula (II):

wherein: m is an integer greater than 0; and each of R₁, R₂, R₃, R₄, R₅,and R₆ is independently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs of any of the foregoing.
 17. The electrochromicpolymer of claim 10, wherein at least one of the plurality ofπ-conjugated chromophores comprises a structure of Formula (III):

wherein: m is an integer greater than 0; and each of R₁, R₂, R₃, R₄, R₅,and R₆ is independently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀alkenyl, C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀alkoxyalkyl, C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs of any of the foregoing.
 18. The electrochromicpolymer of claim 10, wherein at least two of the π-conjugatedchromophores have different structures from one another.
 19. Theelectrochromic polymer of claim 10, wherein at least two of theπ-conjugated chromophores exhibit different colors relative to oneanother in the neutral states thereof.
 20. The method of claim 1,further comprising: adjusting a ratio of non-conjugated flexible spacersto π-conjugated copolymer sequences in order to adjust a meltingtemperature of the electrochromic polymer; and at least one of theπ-conjugated copolymer sequences comprise

wherein each of m, n1, and n2 are integers greater than 0, and R and R′is independently selected from hydrogen, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₂-C₃₀ alkylcarbonyl, C₁-C₃₀ alkoxy, C₃-C₃₀ alkoxyalkyl,C₂-C₃₀ alkoxycarbonyl, C₄-C₃₀ alkoxycarbonylalkyl, C₁-C₃₀aminylcarbonyl, C₄-C₃₀ aminylalkyl, C₁-C₃₀ alkylaminyl, C₁-C₃₀alkylsulfonyl, C₃-C₃₀ alkylsulfonylalkyl, C₆-C₁₈ aryl, C₃-C₁₅cycloalkyl, C₃-C₃₀ cycloalkylaminyl, C₅-C₃₀ cycloalkylalkylaminyl,C₅-C₃₀ cycloalkylalkyl, C₅-C₃₀ cycloalkylalkyloxy, C₁-C₁₂ heterocyclyl,C₁-C₁₂ heterocyclyloxy, C₃-C₃₀ heterocyclylalkyloxy, C₁-C₃₀heterocyclylalkyloxy, C₁-C₃₀ heterocyclylaminyl, C₅-C₃₀heterocyclylalkylaminyl, C₂-C₁₂ heterocyclylcarbonyl, C₃-C₃₀heterocyclylalkyl, C₁-C₁₃ heteroaryl, C₃-C₃₀ heteroarylalkyl, andsubstituted analogs thereof.